Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N3/C-Sulfonyl Migration

被引：3

作者：

Bernar, Ivan ^{[1
]}

Blanco-Ania, Daniel ^{[1
]}

Stok, Sophie J. ^{[1
]}

Sotorrios, Lia ^{[2
]}

Gomez-Bengoa, Enrique ^{[2
]}

Rutjes, Floris P. J. T. ^{[1
]}

机构：

[1] Radboud Univ Nijmegen, Inst Mol & Mat, Heyendaalseweg 135, NL-6525 AJ Nijmegen, Netherlands

[2] Univ Basque Country, UPV EHU, Dept Organ Chem 1, POB 1072, Donostia San Sebastian 20080, Spain

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2018年 / 2018卷 / 39期

关键词：

Ynamines; Homogeneous catalysis; Palladium; C-H activation; Synthetic methods; CHIRAL TOLUENE-2; ALPHA-SULTAM AUXILIARIES; 2 DISCRETE NITRILES; C-H BOND; 2+2+2 CYCLOADDITIONS; ARYL ETHERS; YNAMIDES; REARRANGEMENT; 1,1-DIOXIDE; CYCLIZATION; ACTIVATION;

D O I：

10.1002/ejoc.201801062

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35% yields after two steps).

引用

页码：5435 / 5444

页数：10

共 73 条

[1] The evaluation of chiral benzosultams as auxiliaries in asymmetric azidation reaction [J].

Ahn, KH ;

Kim, SK ;

Ham, C .

TETRAHEDRON LETTERS, 1998, 39 (35) :6321-6322

[2]

Alam K., 2017, Angew. Chem, V129, P13572

[3] Divergent C-H Annulation for Multifused N-Heterocycles: Regio- and Stereospecific Cyclizations of N-Alkynylindoles [J].

Alam, Khyarul ;

Hong, Sung Won ;

Oh, Kyung Hwan ;

Park, Jin Kyoon .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (43) :13387-13391

[4]

[Anonymous], ANGEW CHEM

[5]

Baker D. C., 2002, U.S. Patent, Patent No. [6,353,112 Bl, 6353112]

[6] An unexpected two-group migration involving a sulfonynamide to nitrile rearrangement.: Mechanistic studies of a thermal N → C tosyl rearrangement [J].

Bendikov, M ;

Duong, HM ;

Bolanos, E ;

Wudl, F .

ORGANIC LETTERS, 2005, 7 (05) :783-786

[7] Synthesis of Functionalized Allenamides from Ynamides by Enolate Claisen Rearrangement [J].

Brioche, Julien ;

Meyer, Christophe ;

Cossy, Janine .

ORGANIC LETTERS, 2013, 15 (07) :1626-1629

[8] Synthesis of ynamides from formamides [J].

Brückner, D .

TETRAHEDRON, 2006, 62 (16) :3809-3814

[9] TfOH-mediated [2+2+2] cycloadditions of ynamides with two discrete nitriles: synthesis of 4-aminopyrimidine derivatives [J].

Chen, Ping ;

Song, Cai-xia ;

Wang, Wan-shu ;

Yu, Xue-liang ;

Tang, Yu .

RSC ADVANCES, 2016, 6 (83) :80055-80058

[10] Terminal ynamides: synthesis, coupling reactions, and additions to common electrophiles [J].

Cook, Andrea M. ;

Wolf, Christian .

TETRAHEDRON LETTERS, 2015, 56 (19) :2377-2392

← 1 2 3 4 5 6 7 8 →